Red mordant dyestuff and process of making same.



UNITED STATES PATENT OFFICE.

RED MORDANT DYESTU'FF AND PROCESS OF MAKING SAME.

No Drawing.

To all whom it may concern:

Be it known that we, CHARLES DE LA HARPE and ERNST BoDMeR, both chemists, citizens of the Swiss Republic, and residents of Basel, Switzerland, hvave'inVentedNeW Retl Mordant Dyestuffs and a Process of Making Same, of which the following is, a full, clear, and exact specification. I

lVe have found that new red mordant dyestuffs are obtained by condensing an amino-meta-oxybenzoylbenzoic acid substi' 'tuted in the amino group with a'resorcin sultonic acid. The condensation is obtained by warming the compounds together in a suitable medium such as sulfuric acid or bisuliate. The most suitable condensing agent is sulfuric acid, of which the concentration may vary within wide limits; an acid of 50 per cent strength, however, is still applicable. In most cases, nevertheless, it is advantageous to use concentrated acid, because prolonged heating with too dilute an 'cid leads easily to desulfonation. Obviously, it is simplest to sulfonate the resorcin and to add the amino-meta-oxybenzoylbenzoic acid substituted in the amino group to the mass in which the sulfonation is effected, so that the condensation may occur in the same operation. The operations may, however. be separate. This process is applicable to all known monoand di-alkylated, benzylated, ethylbenzylated or phenylated amino-rneta-oxy-benzoylbenzoic acids. The same dyestuffs are obtained whether resor- 35 cinmonosulfonic acid or resorcindisulfonic \acid are employed, this latter reacting, in a surprising manner, with elimination of a sulfo group. Owing to this fact it. is possible to make without ditliculty the new dyestuffs at a ten'iperature below 100 C. in nearly quantitative yield free from interv mixed non-sulfonated product. The new dyestutt's thus obtained are suliorhodols and dye chrome mordanted fibers clear bluish red to yellowish red tints. They are well marked mordant dyestuti's, whose properties in this respect, however are due to the ortho positions of 'a hydroxyl group and of a sult'o group. These new sulforhodols are further characterized by the excellent solu bility of their alkali salts in Water. As they are of interest for cotton printing, a great advantage accrues from the fact .that, in contradiction to the corresponding known Specification of Letters Patent.

Application filed May 4, 1911., Serial No. 624,945.

Patented Sept. 12, 1911.

non-sulfonated products, they do not dye cot-ton without a mordant. In Washing the printedmaterial, therefore. the portions which are not-"printed remain pure white.

As will be seen from the table hereinafter, the morda'nt character of the new dyestuffs may be expressed by the diflerence of their tints on wool with a mordant and without a mordant. The bodies also dye easily cotton chrome-mordanted andprinted with a discharge, the discharged places remaining quite white. They also have aiiinity for a whole series of metallic mordants besides chromium compounds, for instance, iron, aluminium, tin or like compounds. When printed with chrome mordants' on cotton some of these dyestuffs produce a red nothitherto attainable with chrome dyestuffs. The fastness to chlorin of the dyeings thus obtained must be designated surprising, for it exceeds that of the ordinary rhodamins; In respect to the general fastness, they are similar to the ordinary rhodam'insl The tastness to light of the dyeings on wool is remarkable.

The following examples illustrate. the invention:

- Example I: Into a solution of 10 kilos of resorcinolmonosulfonic acid in 60 kilos of' sulfuric acid of 70 per cent. strength are introduced, while stirring, 14 kilos of dimethylamino-meta-oxybenzoylbenzoic acid corresponding to the formula or an equivalent quantity of another amino- .meta-oxybenzoylbenzoje acid substituted in the amino group and the mixture is heated to 90 C. until no further increase in the formationot dyestulf can be observed. The cooled mass is poured into ice-water and the dyestult which separates in flocks is filtered and pressed. By warming with sodium acetate'solution the sulfonated dyestuif can be separated from a little non-sulfonated prodnot which is present and a quite small proportion of a basic lay-product. From the I the formula Example Hi 14 kilos of resorcinoldisulfonic acid are suspended in 60 kilos of sulmixed with 14 kilosof dimethylamino-metaoxybenzoylbenzoic acid, and an equivalent quantity of another aminonetabxybenzoylbenzoic acid substituted in the amino group, while stirrin The mixture is heated to about 90 C. until no further increase of the formation of dyestufi' occurs. After cooling, the mass is poured into ice-water and the dyestull purified and isolated in the manner described in Example I. The same dyestuffs are obtained as are obtained by following Example I. a

The new dyestuffs are brown-red to red powders, easily soluble in the form of their alkali salts to red orange or raspberry red solutions from which mineral acids precipitate them as red flocks or aslustrous brown red crystals,' appearing green by reflected light. The properties of a number of them What We claim is:

1. The described process for the manufacture of red mordant dyestuffs, which consists in condensing an amino-metamxybenzoylbenzoicacid substituted 'in the amino group with a resorcin sulfonic acid.

' 2. The described process for the manu facture of red Inordant dyestufls, which con sists 1n condenslng an alkylamino-metaoxybenzoylbenzoic acid with a resorcinsulfonic acid.

3. The described process for the manufacture of red mordant dyestufis, consisting in condensing a dialkylamino-metaoxybenzoylbenzoie acld wlth a resorcinsulfonic acid.

- '4. As new products the described dyestuffs, resulting from the condensation of a resorcin sulfonic acid with an aminome'taoxybenzoylbcnzoic acid substituted in the amino group and constituting in dry state brownrcd to'red powders easily soluble in waterin form of their alkali salts to solutions colored from red orange to raspberry red and showing agreen fluorescence, from which they are precipitated by mineral acids, soluble in concentrated sulfuric acid with a citron yellow to a brown red coloration turning to rose or yellow orange on additionof water, and dyeing unmordanted wool and chromed wool or cotton orange to magenta red tints of excellent fastness to chlorin and light.

In Witness whereof we have hereunto signed our names this 24th day of April 1911, in the presence of two subscribing witnesses.

CHARLES DE LA HARPE. ERNST BODMER.

Witnesses:

KMAND Rrrrnn, Annonn Znnnu. v

20 furic acid of 66 Baum specific gravity and appear in the table hereinafter.

' Color of solution Dyeing on wool Dyeing on No. Dyestufi made fromof alkali salt. 501mm acid without a chromed wool in water. in (mm mordant. or cotton.

1 1.' Dimethylamino-meta-oxybenzoylben- Scarlet, green Citron yeliow.'.. Rose.......l Yellowish red... Red.

zoic acid+resorcinsulionic acid. fluorescence.

p 2. Di-ethylaminoanetabxybenzoylbenzoie Scarlet, some- Yeliow Rose..- Yellowish red. i Red, blncr and acid+resorclnsulionic acid. what is l act more vivid m ore vi v i d than 1, green than 1. than i.

fluorescence.

3. Mono-ethglamino-meta-oxyoenzoylbon- R e d oran ge Citron yeilow.. Yellow orange. Orange Orange red.

zoio eoi l-msorcinsulionic acid. green fluorescanoe. v v 4. -Phen laminaduets-oxybexiioylbenzoic Raspberry red, Brown red Rose Magenta red..... Magenta red, aci +resorcinsuiionic acid. green fluotesbluer. p canoe.

5. Ethylbsnzylamino meta oxybenzoyi- R e d oran go Yellow Red orange Orange R ed oron go, 7 benzoic aoid+zesoxcinsuli0n c acid. green fluoresredder than 3.

' I cence. 

